School of Chemistry and Chemical Engineering, Nanjing University , Nanjing 210093, People's Republic of China.
J Org Chem. 2014 May 2;79(9):3847-55. doi: 10.1021/jo500192h. Epub 2014 Apr 11.
An iron-catalyzed oxidative esterification reaction between unactivated C(sp(3))-H bonds from symmetric and asymmetric ethers and carboxylic acids using di-tert-butyl peroxide (DTBP) as the oxidant via a cross dehydrogenative coupling (CDC) reaction was established, which tolerates a wide range of cyclic ether substrates to react with aromatic acids and phenylacetic acid, providing an efficient method for the preparation of α-acyloxy ethers with good to excellent yields. Intermolecular competing kinetic isotope effect (KIE) experiments were also carried out, which indicate that C(sp(3))-H bond cleavage may be the rate-determining step of this CDC reaction.
建立了一种铁催化的氧化酯化反应，通过交叉脱氢偶联（CDC）反应，使用过氧化二叔丁基（DTBP）作为氧化剂，从对称和不对称醚和羧酸中的未活化的 C(sp(3))-H 键进行反应，该反应容忍广泛的环醚底物与芳香酸和苯乙酸反应，为制备具有良好至优异产率的α-烷氧基醚提供了一种有效方法。还进行了分子间竞争动力学同位素效应（KIE）实验，表明 C(sp(3))-H 键的断裂可能是该 CDC 反应的决速步骤。
